US6143205A - Mixtures containing monomers and stabilizers - Google Patents

Mixtures containing monomers and stabilizers Download PDF

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US6143205A
US6143205A US09/117,178 US11717898A US6143205A US 6143205 A US6143205 A US 6143205A US 11717898 A US11717898 A US 11717898A US 6143205 A US6143205 A US 6143205A
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alkyl
mixture
hydrogen
radicals
monomers
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Heinz Friedrich Sutoris
Alexander Aumuller
Hermann Uhr
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BASF SE
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BASF SE
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Priority claimed from DE1996122498 external-priority patent/DE19622498A1/de
Priority claimed from DE1996134470 external-priority patent/DE19634470A1/de
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B63/00—Purification; Separation; Stabilisation; Use of additives
    • C07B63/04—Use of additives
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/20—Use of additives, e.g. for stabilisation

Definitions

  • the present invention relates to mixtures which, in addition to vinyl-containing monomers for preventing their premature polymerization during purification or distillation, also contain at least one nitroxyl and at least one nitro compound, a process for purifying or distilling such monomers without their premature polymerization taking place, and the use of mixtures which contain nitroxyl and nitro compounds for inhibiting the premature polymerization of vinyl-containing monomers.
  • Japanese publication Hei 1-165 534 discloses I-piperidyloxy derivatives as polymerization inhibitors for styrene.
  • U.S. Pat. No. 35 3,733,326 describes the inhibition of the polymerization of vinyl monomers by using free radical precursor compounds.
  • Nitro compounds such as 2-nitro-p-cresol or 2,6-dinitro-p-cresol, are mentioned as polymerization inhibitors in U.S. Pat., No. 4,086,147, 4,105,506 and 4,252,615.
  • U.S. Pat. No. 4,132,602 and 4,132,603 disclose the use of halogenated nitroaromatic compounds for inhibiting the polymerization of vinylaromatics during their distillative working-up.
  • U.S. Pat. No. 5,254,760 describes mixtures of nitroxyl and nitro compounds for stabilizing vinylaromatic compounds during purification or distillation.
  • the nitroxyl and nitro compounds are used in amounts of from 5 to 95% by weight and from 95 to 5% by weight, based on the total amount of the mixture. Since nitroxyl compounds are as a rule very expensive, this stabilizing additive, which must be added continuously in a certain amount to the crude product before working-up, constitutes a cost factor which is not negligible.
  • a further disadvantage of these mixtures is their relatively low efficiency with regard to delaying the polymerization of monomers. If the feed of the inhibitor/crude monomer mixture into the distillation apparatus is interrupted, for example as a result of an operational fault, not only is there a lack of cooling of the column bottom caused by their continuous introduction but in addition, owing to inadequate stabilization, there is an exothermic polymerization with evolution of heat and an associated increase in temperature, which in turn accelerates the polymerization. In extreme cases, extensive polymer formation over a prolonged period may thus render a corresponding purification or distillation unit useless.
  • Preferred mixtures are those which contain from 0.1 to 4.0% by weight of the component (i) and from 99.9 to 96% by weight of the component (ii), based in each case on the total mixture (B).
  • Preferred vinyl-containing monomers (A) are those of the formula (Ia) ##STR1## where: R 1 , R 2 , R 3 and R 4 , independently of one another, are each hydrogen, C 1 -C 6 -alkyl, C 2 -C 6 -alkenyl, unsubstituted or substituted aromatic or heteroaromatic radicals or halogen,
  • the C 1 -C 6 -alkyl radicals include the linear alkyl chains of methyl through ethyl to hexyl as well as the corresponding branched radicals. Furthermore, suitable C 2 -C 6 -alkenyl radicals are ethenyl, propenyl, etc. up to hexenyl and the groups which are branched in the saturated moiety.
  • Examples of both unsubstituted and substituted aromatic or heteroaromatic groups are phenyl, pyridyl, alkylphenyl or alkylpyridyl, such as methylphenyl, methylpyridyl, ethylphenyl or ethylpyridyl, alkenylphenyl or alkenylpyridyl, such as vinylphenyl or vinylpyridyl, carboxyphenyl or carboxypyridyl, formylphenyl or formylpyridyl, sulfophenyl or sulfopyridyl, hydroxyphenyl or hydroxypyridyl, aminophenyl or aminopyridyl, nitrophenyl or nitropyridyl, as well as naphthyl or napthyl substituted by alkyl, alkenyl, carboxyl, formyl, sulfo, hydroxyl, amino or nitropyr
  • examples of monomers to be added are ⁇ -methylstyrene (2-phenyl-prop-1-ene), the two ⁇ -methylstyrene isomers (cis- and trans-1-phenyl-prop-1-ene), ⁇ -ethylstyrene (2-phenylbut-1-ene), the two ⁇ -ethylstyrene isomers (cis- and trans-1-phenylbut-1-ene) up to a-hexylstyrene (2-phenyloct-1-ene) and the two ⁇ -hexylstyrene isomers (cis- and trans-1-phenyloct-1-ene).
  • phenyl or pyridyl radical is substituted by the abovementioned groups, compounds such as ⁇ -methylstyrenesulfonic acid (2-sulfophenylprop-1-ene), ⁇ -methylnitrostyrene (2-nitrophenylprop-1-ene), ⁇ ethyl-styrenesulfonic acid (2-sulfophenylbut-1-ene), ⁇ -ethyl-nitrostyrene (2-nitro-phenylbut-1-ene), the analogous pyridyl monomers or the cis/trans-isomers of the corresponding ⁇ -substituted compounds are obtained.
  • substituted butadienes are also among the monomers which can be obtained. It is possible to use, for example, the compounds 1- or 2-phenylbutadiene, 1- or 2-pyridylbutadiene with the corresponding cis/transisomers on the one hand and, in the case of the pyridyl radical, once again the positional isomers arising from the relative position of the N atom to the pyridyl-vinyl bond.
  • various substituents mentioned further above may occur on the aromatic or heteroaro-matic system.
  • aromatically or heteroaromatically substituted ethylenes such as styrene, vinylpyridine, divinylbenzene, nitrostyrene, styrolsulfonic acids, vinyltoluene and, if desired, isomers thereof may also be used.
  • three of the radicals R 1 , R 2 , R 3 , R 4 are hydrogen and only one is an aromatic or heteroaromatic unsubstituted or substituted group in these monosubstituted ethylenes, i.e. in the order of phenyl, pyridyl, vinylphenyl, nitrophenyl, sulfophenyl and methylphenyl.
  • disubstituted ethylenes in which two or four radicals R 1 , R 2 , R 3 , R 4 are hydrogen and the remaining radicals are aromatic or heteroaromatic groups may also be used.
  • stilbenes such as 4,4'-diaminostilbene, 4,4'-dinitrostilbene, 4,4'-dinitrostilbene-2,2'-disulfonic acid, 4,4'-diaminostilbene-2,2'- disulfonic acid (flavonic acid) or their cis- or trans-isomers. It is of course also possible to use those isomers which differ from one another with respect to the position of the substituent or of the substituents in the aromatic of heteroaromatic system relative to the vinyl group.
  • two of the radicals R 1 , R 2 , R 3 , R 4 are hydrogen and the remaining radicals are nonvicinal radicals, which in this case are also identical, in the order aminophenyl, nitrophenyl, nitrosulfophenyl and aminosulfophenyl.
  • Halogen-containing monomers such as vinyl chloride, vinylidene chloride, vinyl fluoride, vinyl bromide and chloroprene (2-chloro-1,3-butadiene) may also be used in the claimed mixtures.
  • vinyl-containing monomers not only as a mixture with their isomers but also as a mixture with one another, as obtained in the crude product, for example in their preparation.
  • Q is oxygen or --NZ 2 --, ##STR2##
  • Z 2 is hydrogen or C 1 -C 4 -alkyl or, together with Z 3 , is a saturated or unsaturated C 3 -, C 4 - or C 5 -alkylene bridge in which one or two CH 2 groups may be replaced by NH, N(C 1 -C 4 -alkyl), N(C 6 -C 10 -aryl) or oxygen and one or two CH groups may be replaced by N and
  • Z 3 is hydrogen, C 1 -C 4 -alkyl or a radical which, together with Z 2 , is a saturated or unsaturated C 3 -, C 4 - or C 5 -alkylene bridge in which one or two CH 2 groups may be replaced by NH, N(C 1 -C 4 -alkyl), N(C 6 -C 10 -aryl) or oxygen and one or two CH groups may be replaced by N.
  • the monomers (A) of the formula (Ib) which are contained in the novel mixtures may contain oxygen as Q.
  • the vinyl ethers in which Z 1 is C 1 -C 4 -alkyl, i.e. methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl are particularly suitable as a component of the novel monomer compositions.
  • Z 1 is preferably --CO--Z 3 .
  • radicals Z 3 in addition to hydrogen and the stated C 1 -C 4 -alkyl groups are those radicals, which, together with --NZ 2 --, form a saturated or unsaturated 5- to 7-membered ring.
  • ring systems are: ##STR3## in particular the N-pyrrolidinonyl and the N-caprolactamyl radicals.
  • Preferred monomers in the novel compositions are N-vinylformamide, N-vinyl-2-pyrrolidone, N-vinyl- ⁇ -caprolactam and the above-mentioned C 1 -C 4 -alkyl vinyl ethers.
  • N-vinylformamide is particularly preferred among these monomers.
  • Preferred N-oxyl compounds in the novel monomer compositions are those of the general formula (II) ##STR4## where R 5 and R 6 , independently of one another, are each C 1 -C 4 -alkyl, or phenyl or, together with the carbon atom to which they are bonded, are a 5- or 6-membered saturated hydrocarbon ring,
  • R 7 is hydrogen, hydroxyl, amino or an m-valent organic radical bonded via oxygen or nitrogen or, together with R 8 , is oxygen or a ring structure defined under R 8 ,
  • R 8 is hydrogen, C 1 -C 12 -alkyl or, together with R 7 , is oxygen or, together with R 7 and the carbon atom to which they are bonded, forms the following ring structures ##STR5## where, when R 7 together with R 8 forms a common radical, m is 1, R 9 is hydrogen, C 1 -C 12 -alkyl or --(CH 2 ) z --COOR 10 ,
  • R.sup. 10 are identical or different C 1 -C 18 -alkyl radicals
  • k 0 or 1
  • z and p independently of one another, are each from 1 to 12 and
  • n 1 to 100.
  • R 5 and R 6 may be C 1 -C 4 -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl or together may form a tetra- or pentamethylene group.
  • R 5 and R 6 are each preferably methyl.
  • radicals R 8 are hydrogen, the abovementioned C 1 -C 4 -alkyl groups and pentyl, sec-pentyl, tert-pentyl, neopentyl, hexyl, 2-methylpentyl, heptyl, 2-methylhexyl, octyl, isooctyl, 2-ethylhexyl, nonyl, 2-methylnonyl, isononyl, 2-methyloctyl, decyl, isodecyl, undecyl, isoundecyl, dodecyl and isododecyl, (the names isooctyl, isononyl and isodecyl are trivial names and originate from the carbonyl compounds obtained by the oxo synthesis; cf. Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, Vol. A1, Pages 290-293, and Vol. A10, Pages 2
  • p is preferably from 6 to 12, particularly preferably 9.
  • z is preferably from 1 to 4, particularly preferably 2.
  • R 9 examples of suitable radicals R 9 in addition to hydrogen are the abovementioned C 1 -C 12 -alkyl groups.
  • R 9 is preferably hydrogen, C 1 -C 4 -alkyl or (CH 2 ) z --COO(C 1 -C 6 -alkyl), particularly preferably --CH 2 --CH 2 --COO(CH 2 ) 11 --CH 3 and --CH 2 --CH 2 --COO(CH 2 ) 13 --CH 3 .
  • R 10 may be, for example, one of the abovementioned C 1 -C 12 -alkyl groups or tridecyl, isotridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl or octadecyl. Dodecyl and hexadecyl are preferred.
  • Preferred monovalent organic radicals R 7 bonded via oxygen are hydroxyl and (C 1 -C 4 )-alkoxy groups, for example methoxy, ethoxy, propoxy or tert-butoxy.
  • Preferred m-valent radicals R 7 are, for example, the following radicals ##STR6## where R 11 is C 1 -C 12 -alkyl or --(CH 2 ) z --COOR 10 ,
  • R 12 is hydrogen or C 1 -C 18 -alkyl
  • R 13 is C 1 -C 18 -alkyl, vinyl or isopropenyl
  • R 14 is C 8 -C 22 -alkyl
  • R 15 is hydrogen or an organic radical as usually formed in the free radical polymerization of the starting monomers
  • k 0 or 1
  • x is from 1 to 12
  • n is an even number m.
  • R 7 is one of these radicals
  • R 8 is preferably hydrogen.
  • m may be from 1 to 100.
  • m is preferably 1,2,3,4 or a number from 10 to 50, mixtures generally being used especially in the case of the oligomeric or polymeric radicals R 7 .
  • R 11 are the same radicals as stated for R 9 .
  • R 11 is preferably C 1 -C 4 -alkyl.
  • R 12 in addition to hydrogen are the same radicals as have been stated for R 10 .
  • R 12 is preferably hydrogen.
  • Suitable radicals R 13 are vinyl, isopropenyl and C 15 -C 17 -alkyl.
  • radicals R 14 are the abovementioned C 8 -C 18 -alkyl radicals and nonadecyl, eicosyl, uneicosyl and doeicosyl. Mixtures of different radicals R 14 , which differ in the length of the carbon chain are preferred.
  • R 15 is hydrogen or an organic radical as formed in the free radical polymerization of the starting monomers, for example a radical which is formed from the polymerization initiator or from a radical occurring as an intermediate, or another such radical as is familiar to a person skilled in the art.
  • Preferred nitroxyl compounds as component (i) of the novel monomer compositions are also the following:
  • nitroxyl compounds described can be prepared from the corresponding piperidine compounds by oxidation, for example with hydrogen peroxide. Details of this oxidation are stated, for example, in the prior German patent application 195 101 84.7.
  • the secondary amines which carry no hydrogen atoms on the ⁇ -carbon atoms, such as piperidine compounds, and their preparation are generally known. Since the oxidation reactions do not always go to completion, the piperidine compounds serving as starting compound and partially oxidized intermediates may also be present in the novel monomer compositions.
  • Monomer mixtures contain, as component (ii), at least one aromatic nitro compound of the formula (III) ##STR7## where R 16 , R l7 , R 18 and R 19 , independently of one another, are each hydrogen, C 1 -C 6 -alkyl, halogen or a radical of the formula CN, SCN, NCO, OH, NO 2 , COOH, CHO, SO 2 H or SO 3 H,
  • suitable compounds are 1,3-dinitrobenzene, 1,4-dinitrobenzene, 2,6-dinitro-4-methylphenol, 2-nitro-4-methylphenol, 2,4,6-trinitrophenol, 2,4-dinitro-1-naphthol, 2,4-dinitro-6-methylphenol, 2,4-dinitrochlorobenzene, 2,4-dinitrophenol, 2,4-dinitro-6-sec-butylphenol, 4-cyano-2-nitrophenol and 3-iodo-4-cyano-5-nitrophenol.
  • Aromatic nitro compounds such as 2,6-dinitro-4-methylphenol, 2-nitro-4-methylphenol, 2,4-dinitro-6-sec-butylphenol or 2,4-dinitro-6-methylphenol, in which one of the radicals R 16 , R 17 , R 18 and R 19 is nitro, one is hydroxyl and one is C 1 -C 6 -alkyl, are preferably used.
  • one or more costabilizers selected from the group consisting of the aromatic nitroso compounds, phenothiazines, quinones, hydroquinones and their ethers, phenols and their ethers, hydroxylamines and phenylenediamines may be added to the mixture (B) in addition to the components (i) and (ii).
  • aromatic nitroso compounds examples include p-nitrosophenol, p-nitroso-o-cresol and p-nitroso-N,N'-diethylaniline.
  • these compositions contain an effective amount of the mixture (B), which in general means from 0.0002 to 5, preferably from 0.0005 to 0.5% by weight, based in each case on the total amount of the monomer composition, of the mixture (B).
  • the mixtures (B) can of course also contain mixtures of different novel nitroxyl and nitroso compounds and of the stated costabilizers.
  • Mixture (B) can be added to the monomers before or during the purification or distillation in an effective amount, in order to suppress premature polymerization. In specific cases, it may also be necessary to add the components (i) and (ii), with or without the addition of one or more of the stated costabilizers, separately and then preferably at different points in space.
  • novel stabilizer mixtures (B) may be used either as such or as a suspension or solution with the aid of suitable diluents. They can be used generally for inhibiting premature polymerization of, preferably, monomers capable of free radical polymerization and display their stabilizing effect in a broad temperature range. They are effective at any conventional storage temperature from -50 to +50° C. and also at elevated temperature as used, for example in the distillation or purification of the monomers.
  • the pressure range of the stabilization process is also not critical.
  • the stabilizers are effective at atmospheric pressure and also at reduced pressure, as used in some distillation processes.

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US09/117,178 1996-06-05 1997-05-28 Mixtures containing monomers and stabilizers Expired - Lifetime US6143205A (en)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
DE19622498 1996-06-05
DE1996122498 DE19622498A1 (de) 1996-06-05 1996-06-05 Mischungen, enthaltend Monomere und Stabilisatoren
DE1996134470 DE19634470A1 (de) 1996-08-27 1996-08-27 Mischungen, enthaltend Monomere und Stabilisatoren
DE19634470 1996-08-27
PCT/EP1997/002758 WO1997046504A1 (de) 1996-06-05 1997-05-28 Mischungen, enthaltend monomere und stabilisatoren

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CN (1) CN1082499C (id)
DE (1) DE59704135D1 (id)
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ID (1) ID17021A (id)
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US6300533B1 (en) * 1999-08-16 2001-10-09 Uniroyal Chemical Company, Inc. Inhibition of polymerization of ethylenically unsaturated monomers
US6342647B1 (en) * 1998-09-09 2002-01-29 Baker Hughes Incorporated Vinyl monomer polymerization inhibition using hindered hydroxylamines
US6379588B1 (en) * 1996-09-23 2002-04-30 Basf Aktiengesellschaft Stabilized monomer composition
US6672903B1 (en) * 2003-01-22 2004-01-06 Ting-Chu Chen Signal-line connector
US20040019247A1 (en) * 1999-02-26 2004-01-29 Basf Aktiengesellschaft Continuous recovery of styrene from a styrene-containing mixture
US20050113625A1 (en) * 1999-12-03 2005-05-26 Uniroyal Chemical Company, Inc. Composition and method for inhibiting polymerization and polymer growth
US20060069219A1 (en) * 2004-09-28 2006-03-30 Vilan Kosover Sulfonated phenols with nitrophenols as polymerization inhibitors
US20060069218A1 (en) * 2004-09-28 2006-03-30 Vilan Kosover Sulfonated nitrophenols as polymerization inhibitors
US20060122341A1 (en) * 2004-12-03 2006-06-08 Vilan Kosover Aromatic sulfonic acids, amines, and nitrophenols in combination with nitroxyl radical-containing compounds or C-nitrosanilines as polymerization inhibitors
US20060178489A1 (en) * 2005-02-04 2006-08-10 Vilen Kosover Means for controlling the exothermic reaction of styrenic monomers with sulfonic acids
US9206268B2 (en) 2011-09-16 2015-12-08 General Electric Company Methods and compositions for inhibiting polystyrene formation during styrene production
US9561997B2 (en) 2013-12-06 2017-02-07 Wacker Chemie Ag Process for preparing vinyl acetate with inhibited by-product formation

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DE19725519A1 (de) 1997-06-17 1998-12-24 Basf Ag Stoffmischung, enthaltend vinylgruppenhaltige Verbindungen und Stabilisatoren
DE19922103A1 (de) * 1999-05-17 2000-11-23 Basf Ag Stoffmischungen, enthaltend vinylgruppenhaltige Verbindungen und Stabilisatoren
ATE307789T1 (de) 1999-12-02 2005-11-15 Crompton Corp Polymerisationsinhibierung von ungesättigten monomeren
AR029410A1 (es) 1999-12-02 2003-06-25 Crompton Corp Metodo para inhibir la polimerizacion prematura de monomeros etilenicamente insaturados y composiciones de los mismos
US6403850B1 (en) 2000-01-18 2002-06-11 Uniroyal Chemical Company, Inc. Inhibition of polymerization of unsaturated monomers
US6344560B1 (en) * 2000-05-03 2002-02-05 Uniroyal Chemical Company, Inc. Nitroaromatic solubilizer for nitroxyls in aromatic solvents
KR100812038B1 (ko) 2000-10-16 2008-03-10 유니로얄 캐미칼 캄파니, 인크. 중합 억제제로서 퀴논 알키드와 니트록실 화합물의 블렌드물
US6685823B2 (en) 2000-10-16 2004-02-03 Uniroyal Chemical Company, Inc. C-nitrosoaniline compounds and their blends as polymerization inhibitors
DE102009027115A1 (de) 2009-06-23 2010-12-30 Wacker Chemie Ag Verfahren zur Herstellung von Vinylacetat

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EP0906257B1 (de) 2001-07-25
CN1082499C (zh) 2002-04-10
MY117369A (en) 2004-06-30
JP2000511545A (ja) 2000-09-05
EP0906257A1 (de) 1999-04-07
ID17021A (id) 1997-12-04
CN1211968A (zh) 1999-03-24
TW434308B (en) 2001-05-16
EP0906257B2 (de) 2010-04-07
DE59704135D1 (de) 2001-09-13
JP3401018B2 (ja) 2003-04-28
ES2162299T3 (es) 2001-12-16
WO1997046504A1 (de) 1997-12-11

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